Printing ink vehicle



United States Patent '0 PRINTING INK VEHICLE Walter W. Mock, Rutherford, N. J., and Richard H. Bidle, Chicago, Allen G. Corliss, St. Charles, and Harold E. Phifer, Riverside, lll., assignors to Interchemical Corporation, New York, N. Y., a corporation of Ohio No Drawing. Application June 18, 1954 Serial N0. 437,892

I 3 Claims. (Cl. 106-239) This invention relates to varnishes which are particularly adapted for use as vehicles for printing inks; more particularly the invention relates to varnishes containing zinccalcium resinate dissolved in a suitable solvent and to inks made therefrom.

Heretofore, it has been known to prepare ink varnish vehicles which comprise zinc-calcium resinate solutions. Such varnishes can be made by the fusion method, i. e. reacting rosin with the appropriate zinc and calcium compounds in the absence of solvent and then dissolving the resulting resinate in a suitable solvent, or they can be made by a two step solvent method, i. e. by reacting rosin in solution with the appropriate zinc compound and then in a second step with'the calcium compound. Neither of these methods gives a varnish that is particularly desirable for use in ink varnish vehicles which include ethyl cellulose as an additional binder in the varnish vehicle. Such resinates, when dissolved in low solvency hydrocarbon solvents such as lactol spirits do not have the ability to hold ethyl cellulose in solution.

We have now discovered an improved process for making zinc-calcium resinate varnishes, using low solvency hydrocarbon solvents, that are compatible with ethyl cellulose and hold the ethyl cellulose in solution.

In accordance with the method of our invention we react calcium hydroxide and zinc oxide with rosin dissolved in a low solvency hydrocarbon solvent in a one reaction step. The reaction is carried out under autogenous pressure by heating the reaction mixture in an enclosed vessel to the desired reaction temperature, heating being continued until all of the calcium and zinc compounds have combined with the rosin. The reaction temperature may vary over rather wide limits, however, we prefer temperatures on the order of 250 to 400 F. The time for complete reaction will of course, be less, the higher the reaction temperature is maintained.

Preferably the reaction is carried out in the presence of conventional catalyst, such as low molecular weight aliphatic monocarboxylic acid. Acetic acid is a typical and preferred catalyst.

Other conventional additives are advantageously included in the reaction mixture. For instance aldehydes, such as a small amount of formaldehyde, tends to prevent crystallization of the resinate.

The following ratios are preferred ratios of reactants used in the process of the present invention:

Formaldehyde (paraformaldehyde) 3 to 4 ICC oil rosin D, which has a melting point of 169190 F- (ring and ball method), an acid number of 160-170, a saponification number of 168-178, and an unsaponifiable content of 4.5 to 7%.

Typical specific examples of the invention are:

Example 1 An ink varnish was prepared from: Parts Acintol R tall oil rosin D 48.92

Lactol spirits (hydrocarbon solvent, boiling range 198' to 242 F., dimethyl sulfate value 16%) 24.46

Calcium hydroxide 1.37 Zinc oxide 2.69 Glacial acetic acid V 0.10 Paraformaldehyde 1.61

The above ingredients were mixed and heated in an ena closed vessel provided with a trap for collecting water.

Heating was continued at 285 F. to 360 F. until the. reaction was complete as evidenced by the rate at which water is being collected in the water trap. As water is removed the temperature increases so that by the time the reaction is complete, about three hours, the temperature is at the maximum. Although the process was carried out in such manner that the internal pressure of the system never exceeded about 55 pounds per square inch, this was due to the fact that the equipment used was not designed for higher pressure and not to a limitation on the process itself.

The reaction mixture was cooled to about 150 F. and then Parts Lactol spirits Ethyl cellulose (46.8-48.5% ethoxy, centipoise grade) Ethyl alcohol Example 2 A typical ink formulation using the above varnish, is as follows:

Parts by weight Benzidine yellow 3.00

Chrome yellow 8.00 Clay 12.00 Xylol 1.00 Varnish, from Example 1 74.00 Lactol spirits 2.00

The varnish used in the above formulation is varnish containing 2.15 parts of ethyl cellulose. Although the varnish which does not contain ethyl cellulose can be used in making inks, we prefer to use ethyl cellulose to obtain the best inks.

7 Example 3 A red ink is prepared in accordance with the invention by suitably mixing the following ingredients:

' A blue inl i' is 'prepa'r'edlin accordance witlithe' invention by-suitablymixingiz" a i V ia s Pens} Mil'oii blue i 12,50 Xylol a w 17711 3 Varnish'froni Eit'ai-nple IL. 83.00 Lactol spirits a 11:1 3

It will berunderstood thatuthe practiceuof. thepresent invention is not to belirnited totl'ie' specific'exaniples disclo'sed above but that rvarious' modifications may-bemade as it is defined in the appenddclaimsl 1; The me'tliod' orpreearingia zrnc calcium resina'te therein Without departing from the;s'c'o'pef of the -invention luoii afts orrdsindisselvedin"5016 0'. parts ofa hydr carbon'sblvenfc'apabl'e" oflioldii'ig' the zinc calcium resin- E5523; sav

varnish for use in printing inks consisting of, reacting 100 parts of rosin dissolved in 50 to 150 parts of a hydrocarbon solvent capable of holding the zinc calcium resinate and ethyl cellulose in solution, with 1.0 to 5.5 parts calcium hydroxide and 5.0 to 15.0 parts zinc oxide and 3 to 4 parts formaldehydein the presence of acetic acid as a catalyst, at a temperature of about 250 F. to 400 F. under autogenou's*pre'ssure until all the zinc and calcium compounds *have'reac-ted; V Q 7 V 3. The method of preparing a varnish for use in print; ing inks consisting ofireaetin-glDQFPai ts of; a:- commercial grade" of rosin"obtained-fromgsulfiteiwasteliquor and'glizi'vihg a rnelting'fpoi'ntofl69:19.0 (tin'gaiidblhiietli'cSdL an acid number-"015160470; a s'ap'onification number of '1 69-178, s and an aunsaponifiable; content i of 4:5 to 7 dissolved in 50 to 150 parts of a H-ydrocarbon solvent having a boiling rangeof 198? to,242"- -F.- and a dimethyl sulfate value of 16%, with 110 to STS 'parts calcium hy-'-' droxide, 5.0 to 15.0 parts zinc oxide and 3 to 4 parts formaldehyde,v in% the; presence: of: acetic 1 acid catalyst,

at a -temperature31bout2i0 toe4'00? E;- under autogenousi ate and ethyl cellulosein-solution,iwith.1.0v-tov55'parts" of ealeiumrhydroxid e and 5.0 to 1510 parts: zinc oxide, 35

said' reaction being carried out at a temperatureofabout ZSDF F. to. 4 00" F under autogenous pressure until all the? rind and calcium hydroxide have reacted.

pressure 'until'all tliezinc and calcium compounds-have reacted. '7 7 References Cited in' the file ofthisi'patent UNITED STATES RATENTS 2. The methedof preparing atzincrcalciumresinater. 

1. THE METHOF OF PREPARING A ZINC CALCIUM RESINATE VARNISH FOR USE IN PRINTING INKS CONSISTING OF, REACTING 100 PARTS OF ROSIN DISSOLVED IN 50 TO 150 PARTS OF HYDROCARBON SOLVENT CAPABLE OF HOLDING ZINC CALCIUM RESINATE AND ETHYL CELLULOSE IN SOLUTION, WITH 1.0 TO 5.5 PARTS OF CALCIUM HYDROXIDE AND 5.0 TO 15.0 PARTS ZINC OXIDE, SAID REACTION BEING CARRIED OUT AT A TEMPERATURE OF ABOUT 250*F. TO 400*F. UNDER AUTOGENOUS PRESSURE UNTIL ALL THE ZINC AND CALCIUM HYDROXIDE HAVE REACTED. 